Theoretica Chimica Acta

, Volume 95, Issue 3–4, pp 81–95 | Cite as

A method for population and bonding analyses in calculations with extended basis sets

  • Wenjian Liu
  • Lemin LiEmail author


A method for population and bonding analyses in the calculations with extended basis sets is proposed. The definition and evaluation method of the atomic orbitals in molecular environments (AOIMs) are described. It is shown that the AOIMs can be divided into two subsets, the strongly occupied minimal compact subset {AOIM}B and the very weakly occupied “Rydberg” subset {AOIM}R, according to the orbital population obtained from Mulliken analysis with AOIMs as basis sets. The viewpoint of “molecular orbitals consisting of minimal atomic orbital sets” can be optimally realized in terms of {AOIM}B. The Mulliken population based on AOIMs is reasonable and fairly stable to changes of basis sets. The Mayer bond orders calculated based on {AOIM}B are quite stable to the changes of basis sets; therefore they can be used to measure objectively the contribution of individual atomic orbitals to bonding.

Key words

Population analysis Bond order AOIM Basis set 


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Copyright information

© Springer-Verlag 1997

Authors and Affiliations

  1. 1.State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular EngineeringPeking UniversityBeijingChina

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